Azo dyestuff and process of making the same



Patented Oct. 4, 1932 UNITED STATES asisazze PATENE FFE DANIEL ZINNER, OF SOUTH MILWAUKEE, WISCONSIN, ASSIGNOR, BY MESNE ASSIGN- MENTS, T0 E. I. DU FONT DE NEMOURS & COMPANY, A CORPORATION OF DELAWARE AZO DYESTUFF AND PROCESS OF MAKING THE SAME No Drawing.

tuted -in'the 22 ositi'onsfto various raz a P ,7. P3

olone components. I} Thelgdyestufi's' thus obtained are characterized by greenish-yellow to reddish-orange tintsof-great fastness to light and to milling. v

I haveynow foundthafidyestufis or greenish yellow-to' orange and red shades, of equalfastness to light and tojirii g m 'ejohtained by the' use of the unsubstituted 4;;if diamin'o -diphenylmethane.

fMy invention therefore comprises novelj dyestuffs having the follovvingprobable gen eral formula: H 1

" VN=NYR1 pyrazolone residue or for anyother component, and in which the aryl nuclei are not sub-1 stituted. a

1' The. diamino-diphenylmethane may be prepared by metl1ods analogous to those de-; scribed in -my-c0pending application Serial: No. 290,044 appliedto the substituted dia1nidium carbonate.

tetrazo solution). f

Application filed December 11, 1930. Serial No. 501,672.

no-diphenylmethanes. More particularly, I prefer to prepare them from aniline and formaldehyde in acid solution by the use of A mole of formaldehyde to 1 mole of aniline.

As stated, the groups R and R may be the same .or difi'erent 3-sulostituted:5-py-raz0l0ne residues.=' The lljydrogensmoni it exaromat q' ring-of the pyra zolones may be; substituted byother groups, for exampleg'by alkyl, hal gem alkoXy, sulfoni c acid and the like order to give. the dyestufiflproper the ,(lyefa i, vthe:a y 111 f t QPL Y QZ lon'residueshould contain-atlast bility-imparting, group, such as an SOgH group, or a COOH Without limiting my inyention to anyparticular procedure, the following eiiaiiipl'es' in which parts by weight aregivenyvillserve to 'illustratemy method in its preferred form: Y P lEmamp lej l sl9l8 parts of 4,4-diaini'nodiphenyl meth I ane base are tetrazotizedin the usual manner With 58 parts of hydrochloric acidof'QO". I'B- and 13.8parts of sodiumnitrite'in 200cc: of; Water. The resulting tetrazo'solutjionis run" into a-cooled solution containing 66 parts of -pyrazolone and rendered alkalineith so- (Sodium acetate maybe? substituted for neutralizing the :acid in the:

After stirring for a short; -ti me,; common salt is added-until about a salt solution results, andthe mixture-i is then heated to,

abOutlSO- C; The solution is. cooled some-v What andthe separated dyestufij is filtered: off, Washed With;,a-little Water and dried The product after drying is a yell0W ,poWder' which dyes "Wooland silk in an acid or neutral bath greenish yelloW shades;remarkably fast to-light; and to milling,

The product in its free acid form has most probably the following formula:

E example 2 i 19.8 parts of 4,4-diamino-diphenylmethof 1- (2-chloro-5f-sulfo-phenyl) -3-methyl-f pyrazolone and rendered alkaline with sodium carbonate. The dyestuff is isolated as in' 19.8 parts of 4,4-diamino-diphenylmethane base are tetrazotized as in Example 1,

run into a cooled solution containing 52 parts of 1 (4-sulfo-phenyl)-3-methyl-5-pyrazolone and rendered slightly alkaline with sodium carbonate.

The dyestuft' is isolated as in Example 1. The product after drying is a yellow powder which dyes wool and silk in an acid or neutral bath yellow shades remarkably fast to light and to milling.

Other pyrazolones may similarly be used as coupling components; for instance, any of the pyrazolones mentioned in the'table be low. Again, if for instance unsulfonated phenylmethyl-pyrazolone is used, the result-' ing dyestufi is insoluble in water and may be used as a pigment.

If desired, my tetrazo-diphenyl-methane compound may be coupled first to any other component for instance, naphthol-sulfonic acid or naphthylamine-sulfonic acid, etc., and then coupled to a pyrazolone component. The shade in such a case depends on the other component; In the case of naphthols, it is generally'orange to red. The following additional examples will serve to illustrate the process of preparing unsymmetrical dyestuffs of the above type.

Ewample 4 19.8 parts of 4,4'-dia1nino-diph-enylmethane are tetrazotized in the usual manner with 13.8 parts of sodium nitrite and 58 parts of hydrochloric acid (20 Be) at a temperature of 0 to 5 C. The tetrazo solution is neutralized by the addition of sodium carbonate, sodium bicarbonate or sodium acetate. To this neutralized tetrazo solution is added an alkaline solution containing 32.3 parts of 1-(2,5 -dichloro-4-sulfo-phenyl) -3- methyl-5-pyrazolone. While the coupling is progressing, there is run into the coupling mass a solution of soda ash until the mass becomes alkaline To this intermediate product is then added an alkaline solution containing 22.4 parts of 1-;naphthol-4-sulfo-- acid. The colorchanges from a yellow to orange shade and the coupling'is finished in. a few hours. The mass is'salted to 20 B with common salt and heated at 80- C. After cooling somewhat, the dyestufi is filtered off and dried. It is anorange colored product which dyes silk or wool from an acid or neutral bath bright. orange shades remarkably fast to light and to milling.

E mampl 5 V The procedure in Example 4 can be reversed. That is, to the neutralized tetrazo' solution there is first added an alkalinesolution containing 22.4 parts of l-naphthol- 4-sulfo acid. To this coupling mass, which is completely reacted within a short time, 32.3 parts of 1-(2-5-dichloro-4-sulfo-phc nyl) -3-methyl-5-'pyrazolone is then added and the product isolated as in Example 4. It is identical as to physical appearance and dyeing qualities with the product of Example 4.

Example 6 19.8 parts of 4,4-diamino-diphenylmethane are tetrazotized as in Example 4. To the neutralized tetrazo solution an alkaline solution containing 32.3 parts of 1(2',5-dichloro-4-sulfo-phenyl) f-S-methyl 5 pyrazo lone is added and while the coupling is progressing, a solution; of sodium' carbonate is.

acid or neutral bath yellow shades remark ably fast to light and to milling.

but alsoln hateverstate they exist when ap- The following table illustrates various other novel dyestuffs producible by my inven- I claim as my invention:

1. The process of preparing azo dyestuffs tlon. which comprises coupllng a pyrazolone body Tetrazo component: 4, 4'-diamino-diphenylmethane Coupling components Shade 1- (2', 5'-{iich1oro -4 -sulfo -phenyl) -3-methy1-5- 1-(2,4'-dichloro-5-su1fo-phenyl) -3-methy1-5-pyrazo1one Yellow.

pyrazo one. 7 Do 1-(2'-3-dich1oro-6-su1fo-phenyl)-3-methy1-5-pyrazo1one Do. 1-(2,5-dichloro3-sulfo-pheny1)-3-methy1-5-pyrazo1one Do. 1-(4-su1fo-phenyl) 3-methy1-5-pyrazo10ne Do. 1-pheny1-3-methy1-5-pyrazolone Do. 1-(4-methy1'6-sulfo-pheny1)-3-inethy1- Do. 1-(2-methoxy-4-su1fo-phenyl)-3-methy1-5-pyrazo1one. Do. Methyl ketole, or its sulfonic acid Do, Aceto'acet-anilide Do. Phenol or cresol, then treat the dye with toluol-sulfo-chlorlde. Do. Mono-acetyl-meta-phenylene-diamine D0, Mono-acetyl-meta-to1uylene-diamine Do. v 143' or 4-carboxy-pheny1)-3-methy1-5-py1'azo1one Do I Beta-naphthol Yellowish-orange. Beta-naphthol-su1fonic acids Orange, Alpha-naphthol-sulfonic acids Do. 2-amino-5-naphtho1-7-sulfonic acid Do, 1-amino-8-naphtho1-3,fi-disulfonic acid or its N-substitution deriva- Red.

tives (such as benzoyl, acetyl or toluene-sulionyl) l-amino-8-naphtho14-sulfonic acid or l-amino-8-naphthol-2,4-disul- Do.

ionic acid. 2-amino-8-naphthoL6-su1fonic acid or its N-substitution derivatives Reddish-brown. (such as benzoyl, acety], or toluene-sulfonyl). -v i r g g V a It will be understood-{of course, that the above table does not iihaust the field of applicability of my, intention, but is submitted merely for illustrative purposes.

Instead of 1 (2'55' dichloro 4: sulfo phenyl) -3-methyl-5-pyrazolone in said table, any other pyrazoloneinay be used as the R ompon nt vents Lathe c m io s rf p o ib wi i fl ei'scbr efif eit tibn, r i di ia-tha as o t e compo en s 21 W a -pjrra zolonez derivative? Instead :of "the -3- methj l pyrazolones mentioned, the cor Y sp on ding 3-carboirii p yraz olones niaj he used.

It is to bell-understood in the iollowing claims that the orderofcoupl'ing be reversed. Thus the'coupling ivith the and R components may be interchanged in each case within the scope of the claims/" In the claims below, it shouldibe understood that where new products, dyestufi's, or articles of manufacture arezclaimed, mean to include thoselaodies not only in substance plied to materialdyed, printedQor pigmented therewith. Y

seesaw the P i art to a compound the following able general formula/i R is an organic acid residue or th no of an organic coupling'oomponent, and in which the phenylene nuclei contain no further substituents. 1 g

2. The process of pifeparing azo dyestuffs which comprises coupling a pyrazolone body to a 4,4J-tetrazo-diphenylmethane compound having no further sulostituents in the phenylene nuclei and in Whichiat least one of the diazo groups is free t'o couple to organic components. 7

WlllC comprises couplinglt lTIF diamino-diphenylmethane' to a pyrazolone body and to a second coupling component.

4. The process of preparing azo dyestuffs which comprises coupling tetrazotized 4,4-

diamino-diphenylmethane to a pyrazolone 77 body and to a naphthol body.

5. The process of preparing azo dyestuffs which comprises coupling tetrazotized 4,4-

diamino-diphenylmethane to two "different pyrazolone bodies. I

6. The process of preparing azo dyestuffs which comprises coupling tetrazotized 4,4='-- diamino-diphenylmethane to 'substantially two moles of a pyrazolone body.

7 The process of preparing azo dyestuffs which comprises coupling tetrazotized 4,4- diamino-diphenylmethane to two difl'erent pyrazolone bodies,wone of which is 1-(2,5-

dichloroi sulfo-phenyl) 3-methyl-5-pyrazolone. I 7

' 8. The process of preparing azo dyestuffs which comprises coupling tetrazotized 4,4- diamino-diphenylmethanei to substantially two moles of 1-(2,5 dichloro-4-sulfophenyl) -3-methyl-5.-pyrazolone.

9. As new articles of manufacture, a-Zo dyestufis of the following probable general""' formula v N N-Ri in which one of the members R and R is a pyrazolone body and the other member is the same or a different pyrazolone body or any other component.

10. As new articles of manufacture, azo dyestuffs having the following probable gen- 0 eral formula in which i and R2 are the same or diff pyrazolone bodies. c.

feral formula:

11. As new 'articlesof manufacturefa zo dyestu'flsof the following probable generalformula:

CH5 i 1' 7 N=N+R p in which R lis 1- (2,5 -dichloroA sulfophenyl)'-3-methyl-5-pyraZolone, and. R2 is the Same or a di'lferent' pyrazolone body).

13. As a new article of manufacture, a dye stufi having, in the form of its free acid,jthefollowing pro l fo m l 0y NO SOaH N=NCH-OO said dyestuif dyeing wool and silk from an acid or neutral bath in yellow shades fast to light and to milling. v

In testimony whereof Ihave hereunto sub-o scribed my name at'Carrollville, Milwaukee County, Wisconsin.

DANIEL ZINNE J 

